JPS58222133A - Propylene polymer composition having improved coatability - Google Patents

Propylene polymer composition having improved coatability

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Publication number
JPS58222133A
JPS58222133A JP57106353A JP10635382A JPS58222133A JP S58222133 A JPS58222133 A JP S58222133A JP 57106353 A JP57106353 A JP 57106353A JP 10635382 A JP10635382 A JP 10635382A JP S58222133 A JPS58222133 A JP S58222133A
Authority
JP
Japan
Prior art keywords
styrene
propylene polymer
block copolymer
weight
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP57106353A
Other languages
Japanese (ja)
Inventor
Shigeru Ibata
井端 茂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Petrochemical Co Ltd
Original Assignee
Mitsubishi Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Petrochemical Co Ltd filed Critical Mitsubishi Petrochemical Co Ltd
Priority to JP57106353A priority Critical patent/JPS58222133A/en
Publication of JPS58222133A publication Critical patent/JPS58222133A/en
Pending legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To provide the titled polymer compsn. which gives moldings having good rigidity and excellent coating film-adherability in the initial stage of coating, by blending a crystalline propylene polymer, styrene polymers and finely divided calcium carbonate. CONSTITUTION:28-85wt% crystalline propylene polymer such as a propylene/ ethylene block copolymer having an ethylene unit content of 2-20wt% and an MFR of 0.5-40g/10min, 3-30wt% styrene/isoprene block copolymer and/or styrene/butadiene block copolymer (pref. SIS having a weight radio of styrene to isoprene of 12/88-25/75), 2-5wt% styrene polymer having an MW of 50- 500,000 and 10-40wt% fine calcium carbonate powder having an average particle size of 0.05-1mu (pref. surface-treated with a higher fatty acid) are blended together.

Description

【発明の詳細な説明】 本発明は、塗装初期の塗膜付着性の外、塗膜付着性の耐
久性が良好で、かつ剛性の良好なプロピレン重合体組成
物に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a propylene polymer composition that has good coating film adhesion at the initial stage of coating, has good durability of coating film adhesion, and has good rigidity.

プロピレン重合体は、優れた品質と比較的安価なことか
ら広く利用されているが、分子構造上極性がなく、かつ
結晶性が高いため塗装性が極めて不良であることが欠点
の一つとなっている。
Propylene polymer is widely used due to its excellent quality and relatively low cost, but one of its drawbacks is that it has no polarity due to its molecular structure and is highly crystalline, making it extremely poor in paintability. There is.

この欠点を解消するために、プロピレン重合体成形品の
表面をクロム酸混液、有機溶剤や火焔、放電等で処理す
る方法が行なわれている。この方法は、作業性、廃液処
理、作業環境等に難点があって打着しく力いのマ、素材
自体を改善する方法が提案され、例えばプロピレン重合
体にエラストマーを配合する方法が知られているが、剛
性が低下するので、更に無機充填剤を添加する必要があ
り、この無機充填剤を無造作に加えると、プロピレン重
合体の有する低密度、光沢、肌触9感等の優れた点を損
ねるので好ましくかい。
In order to overcome this drawback, a method has been used in which the surface of the propylene polymer molded article is treated with a chromic acid mixture, an organic solvent, flame, electric discharge, or the like. This method has drawbacks in terms of workability, waste liquid treatment, work environment, etc., and is difficult to adhere to and is difficult to use.However, methods to improve the material itself have been proposed, such as a method of blending an elastomer with propylene polymer. However, since the rigidity decreases, it is necessary to further add an inorganic filler, and if this inorganic filler is added casually, the advantages of propylene polymer such as low density, gloss, and texture will be lost. Is it preferable because it will cause damage?

また、プロピレン重合体に特異なゴムと特異な無機充填
剤を添加したり、ゴムとスチレン系樹脂を添加したりす
る方法も知られているが、これらは、最近の高度な要求
性能を満足するKは、未だ十分でない場合が多い。
There are also known methods of adding specific rubber and specific inorganic fillers to propylene polymers, or adding rubber and styrene resins, but these methods do not meet the recent high performance requirements. K is still insufficient in many cases.

本発明は、上記の欠点を解消することを目的としており
、プロピレン重合体に特定成分を所定量配合することに
より、意外にも電装初期の塗膜付着性の外、塗膜付着の
耐久性が良好で、かつ剛性の良好なプロピレン重合体組
成物が得られることが判明して為されたものである。
The purpose of the present invention is to eliminate the above-mentioned drawbacks, and by blending a specific amount of a specific component into a propylene polymer, it surprisingly improves not only the adhesion of the paint film at the initial stage of electrical equipment, but also the durability of the paint film adhesion. This was done based on the discovery that a propylene polymer composition of good quality and good rigidity could be obtained.

すなわち本発明は、下記の(A)〜0成分からなること
を特徴とする塗装性の改良されたプロピレン重合体組成
物である。
That is, the present invention is a propylene polymer composition with improved paintability, characterized by comprising the following components (A) to 0.

(4)結晶性プロピレン重合体25〜85重量多色)ス
チレソーインプレンブロック共重合体および/またはス
チレン−ブタジェンブロック共重合体3〜30重量% C)スチレン系重合体2〜5重量% 0 平均粒径0.05〜1.0μの微粒炭酸カルシウム
10〜40重量% 本発明組成物は、成形品としたとき、その表面に処理を
施さなくても、市場からの要求性能の高度化に対応でき
る塗装性と良好な剛性を有しているので、自動車、家電
、容器、雑貨等の広い分野での利用が可能である。
(4) Crystalline propylene polymer 25-85% by weight Polychromatic) Styreso-imprene block copolymer and/or styrene-butadiene block copolymer 3-30% by weight C) Styrenic polymer 2-5% by weight 0 10 to 40% by weight of fine particles of calcium carbonate with an average particle size of 0.05 to 1.0 μm When the composition of the present invention is made into a molded product, it can meet the demands of the market for sophisticated performance without any surface treatment. It has paintability and good rigidity that can be applied to various applications, so it can be used in a wide range of fields such as automobiles, home appliances, containers, and miscellaneous goods.

本発明で用いる上記囚成分である結晶性プロピレン重合
体は、プロピレン単独結晶性重合体;エチレン、フテン
ー1、ペンテン−1、ヘキセン−1,4−メチルペンテ
ン−1等地のα−オレフィンまたは酢酸ビニル等のビニ
ルエステルと過半重量のプロピレンからなるランダムな
いしブロック共重合体ニアクリル酸、メタクリル酸、マ
レイン酸、イタコン酸等の不飽和有機酸類(エステル、
アミン、アミド、塩、無水物等誘導体も含む)またはビ
ニルトリメトキシシラン等のビニルシランなどでプロピ
レン重合体をグラフト処理したもの等である。
The crystalline propylene polymer which is the above-mentioned prison component used in the present invention is a propylene homocrystalline polymer; an α-olefin such as ethylene, phthene-1, pentene-1, hexene-1,4-methylpentene-1, or acetic acid. Random or block copolymers consisting of vinyl esters such as vinyl and a majority of propylene Unsaturated organic acids (esters,
(including derivatives such as amines, amides, salts, anhydrides, etc.) or propylene polymers grafted with vinyl silanes such as vinyltrimethoxysilane.

中でも、プロピレン単独重合体、他のα−オレフィンを
2〜20重量%含有したプロピレン−α−オレフィンブ
ロック共重合体が良く、とりわけエチレンを2〜20重
量%含有し、MFRo、s〜402/10分のプロピレ
ン−エチレンブロック共重合体が好ましい。
Among these, propylene homopolymers and propylene-α-olefin block copolymers containing 2 to 20% by weight of other α-olefins are good, especially propylene-α-olefin block copolymers containing 2 to 20% by weight of ethylene and having a MFRo, s to 402/10. A propylene-ethylene block copolymer of 50% is preferred.

このような結晶性プロピレン重合体は通常市販のものか
ら適宜選択することができる。
Such a crystalline propylene polymer can be appropriately selected from commercially available products.

また、本発明で用いる(B)成分は、スチレン−イソプ
レンブロック共重合体および/またはスチレン−ブタジ
ェンブロック共重合体である。
Moreover, the component (B) used in the present invention is a styrene-isoprene block copolymer and/or a styrene-butadiene block copolymer.

ここで、スチレン−イソプレンブロック共重合体(SI
S)は、公知の方法(例えば特公昭42−17492号
公報)で得られるスチレンとイソプレンがブロック状に
共重合したゴム状物質であり、スチレンとイソプレンの
比率′(重量比)は10/ 90 = 40 / 60
のものである。
Here, styrene-isoprene block copolymer (SI
S) is a rubbery substance in which styrene and isoprene are copolymerized in block form by a known method (for example, Japanese Patent Publication No. 42-17492), and the ratio of styrene to isoprene (weight ratio) is 10/90. = 40/60
belongs to.

トリわけ、スチレンとイソプレンの比率(重量比)が1
2/88〜25/75のものが好ましい。
The ratio (weight ratio) of styrene and isoprene is 1.
A ratio of 2/88 to 25/75 is preferred.

SISは通常市販のものから選ぶことができる。SIS can usually be selected from commercially available products.

マタ、スチレン−ブタジェンブロック共重合体(SBS
)は、スチレンとブタジェン−ニブロック状に共重合し
たゴム状物質であり、スチレンとブタジェンの比率(重
量比)が20/80〜60/40のものである。とりわ
け、スチレンとブタジェンの比率(重量比)が30/7
’O〜5・0150のものが好ましい。SBSは市販の
ものから適宜選ぶことができる。
Mata, styrene-butadiene block copolymer (SBS
) is a rubbery substance copolymerized with styrene and butadiene in the form of niblock, and the ratio (weight ratio) of styrene and butadiene is 20/80 to 60/40. In particular, the ratio (weight ratio) of styrene and butadiene is 30/7.
'0~5.0150 is preferred. SBS can be appropriately selected from commercially available products.

本発明においては、塗装性の点で、SISの方がSBS
より好ましい。
In the present invention, SIS is better than SBS in terms of paintability.
More preferred.

 5− また、本発明で用いる上記(C)成分であるスチレン系
重合体は、スチレン、メチルスチレン等のスチレン系モ
ノマー等の単独又は共重合体、過半重量のスチレン系モ
、ツマ−と非スチレン系モノマーとの共重合体、例えば
アクリロニトリル−スチレン共重合体(As樹脂)、ア
クリロニトリル−ブタジェン−スチレン共重合体CAB
S樹脂)等が適当である。分子量は500〜500,0
00のものが好ましく、通常市販のものから適宜選ぶこ
とができる。
5- In addition, the styrenic polymer used in the present invention as the component (C) is a mono or copolymer of styrene, styrene monomers such as methylstyrene, a majority of styrene monomers, styrene monomers, and non-styrene monomers. copolymers with monomers such as acrylonitrile-styrene copolymer (As resin), acrylonitrile-butadiene-styrene copolymer CAB
S resin) etc. are suitable. Molecular weight is 500-500,0
00 is preferred, and can be appropriately selected from commercially available products.

更に、本発明で用いる上記0成分である炭酸カルシウム
は、平均粒径が0.05〜1.0μ、好ましくけ0.0
7〜0.8μの沈降性ないしけ湿式粉砕による重質の炭
酸カルシウムである。
Furthermore, the calcium carbonate which is the above-mentioned component 0 used in the present invention has an average particle size of 0.05 to 1.0μ, preferably 0.0μ.
It is a heavy calcium carbonate obtained by wet grinding with a sedimentation barge of 7 to 0.8 microns.

平均粒径が0.05μ未満のものは、製造が非能率であ
る上に、組成物での耐衝撃性、外観が悪化して好1L2
くなく、他方、1.0μを越えるものけ、塗装性、耐衝
撃性が充分でない。
If the average particle size is less than 0.05μ, the production is inefficient, and the impact resistance and appearance of the composition deteriorates, making it undesirable.
On the other hand, if the thickness exceeds 1.0μ, the paintability and impact resistance are insufficient.

ここで平均粒径は、液相沈降方式の光透過法に基すき、
粒度分布測定装置例えば高滓製作所製C6− P型を用いて測定された粒度の累積分布曲線の50係の
点の値である。
Here, the average particle size is based on the liquid phase sedimentation method light transmission method.
The value is the value at the 50th coefficient of the particle size cumulative distribution curve measured using a particle size distribution measuring device, for example, Model C6-P manufactured by Takasu Seisakusho.

炭酸カルシウムは、分散性、成形加工性等の向上の目的
で表面処理[、たものを用いるのが好ましい。表面処理
としては、高級脂肪酸、高級脂肪酸金属塩、シランカッ
プリング系、有機チタネート系等の処理が打着しい。
It is preferable to use calcium carbonate that has been surface-treated for the purpose of improving dispersibility, moldability, etc. Preferred surface treatments include higher fatty acids, higher fatty acid metal salts, silane coupling systems, organic titanate systems, and the like.

これらの(A)〜O)成分の配合割合は、(4)成分が
25〜85重量%、好ましくは45〜78重量%であり
、(B)成分が30〜3重量%、好ましくは20〜5重
量%であり、(C)成分が5〜2重量係であり、0成分
が40〜10重量%、好tL<Fi3o〜15重量%で
ある。
The blending ratio of these components (A) to O) is 25 to 85% by weight, preferably 45 to 78% by weight of component (4), and 30 to 3% by weight, preferably 20 to 3% by weight of component (B). 5% by weight, component (C) is 5 to 2% by weight, component 0 is 40 to 10% by weight, and preferably tL<Fi3o to 15% by weight.

(A成分が25係未満では剛性が劣り、85チ超過では
塗装性が劣る。(B)成分が3チ未満では塗装性が不十
分となり、30%超過では剛性が劣る。
(If the A component is less than 25%, the rigidity will be poor, and if it exceeds 85%, the paintability will be poor. If the (B) component is less than 3%, the paintability will be insufficient, and if it exceeds 30%, the rigidity will be poor.

(C)成分が2%未満では塗装性が劣り、5チ超過では
成形体としたときに表面波−が生じる。0成分が10係
未満では塗装性が劣り、40チ超過では耐衝撃性が劣る
If component (C) is less than 2%, paintability will be poor, and if it exceeds 5%, surface waves will occur when formed into a molded product. If the 0 component is less than 10 parts, the paintability will be poor, and if it exceeds 40 parts, the impact resistance will be poor.

なお、本発明の効果を損なわない範囲で、他の熱可塑性
樹脂、ゴム、無機充填剤、各種安定剤、着色剤等を添加
してもよい。
Note that other thermoplastic resins, rubbers, inorganic fillers, various stabilizers, colorants, etc. may be added to the extent that the effects of the present invention are not impaired.

特に、エチレン−酢酸ビニル共重合体の添加は塗装性の
更なる向上に、またタルク、マイカ、ガラス繊維、ウオ
ラストナイト等の板状や繊維状の無機充填剤の添加は、
耐熱剛性、寸法安定性、成形ソリ抑止性、剛性−耐衝撃
性バランスの向上に有効である。また、核剤として微細
タルクを0.01〜5重量%程度添加すると、側熱剛性
−耐衝撃性バランス、成形性、寸法安定性が向上する。
In particular, the addition of ethylene-vinyl acetate copolymer can further improve paintability, and the addition of plate-like or fibrous inorganic fillers such as talc, mica, glass fiber, and wollastonite can improve paintability.
It is effective in improving heat-resistant rigidity, dimensional stability, molding warpage prevention, and rigidity-impact resistance balance. Further, when about 0.01 to 5% by weight of fine talc is added as a nucleating agent, the side thermal rigidity-impact resistance balance, moldability, and dimensional stability are improved.

本発明組成物は、−軸押出機、二軸押出機、バンバリー
ミキサ−、ロール、フラベンダープラストグラフ、ニー
ダ−等の通常の混線機を用いて製造することができる。
The composition of the present invention can be produced using a conventional mixing machine such as a -screw extruder, a twin-screw extruder, a Banbury mixer, a roll, a Flabender plastograph, or a kneader.

通常は押出機等で混練してペレット状のコンパウンドに
した後、加工に供するが、特殊な場合は、■乃至0成分
を直′l接各種成形機に供給し、成形機で混練しながら
成形することもできる。又、予め炭酸カルシウムを高濃
度に混練l−でマスターバッチとし、それを別途結晶性
プロピレン重合体または特定ゴムで希釈しながらブレン
ドコンパラティングした□す、成形したりすることもで
きる。
Normally, it is kneaded with an extruder etc. to form a pellet-like compound and then subjected to processing. However, in special cases, the components You can also. Alternatively, calcium carbonate may be kneaded to a high concentration to form a masterbatch, which is then blended and comparatively diluted with a crystalline propylene polymer or a specific rubber, and then molded.

本発明組成物は、射出成形、押出成形、圧縮成形等、各
種の方法で成形できその成形品を塗装する。
The composition of the present invention can be molded by various methods such as injection molding, extrusion molding, and compression molding, and the molded product can be coated.

得られた成形品を塗装する前にアルコール、トルエン、
トリクロルエタン等の有機溶剤で表面処理することは、
いつこうに差し支えない。
Alcohol, toluene,
Surface treatment with organic solvents such as trichloroethane
It doesn't matter when.

実施例 第1表に示す配合割合の混合物をスーパーミキサーで混
合後、L/Dが25の二軸押出機で造粒した。
Examples A mixture having the proportions shown in Table 1 was mixed in a super mixer, and then granulated in a twin screw extruder having an L/D of 25.

これを、日本製鋼所製N−100BII射出成形機で2
m厚のシートに成形した。
This was made using an N-100BII injection molding machine manufactured by Japan Steel Works.
It was molded into a sheet with a thickness of m.

塗装試験は、カシュー社製のポリオレフィン用塗料マイ
クロン+4000を、上記シートに厚さ約10μになる
ように吹き付は塗装し、更に同社製ウレタン系塗料(P
H−2)を約30μ厚で塗装後、70℃で3分間加熱乾
燥した。
In the coating test, Micron+4000, a polyolefin paint made by Cashew Co., Ltd., was sprayed onto the above sheet to a thickness of about 10 μm, and urethane paint (P) made by Cashew Co., Ltd.
H-2) was coated to a thickness of about 30 μm, and then heated and dried at 70° C. for 3 minutes.

 9− この塗装面に、縦横それぞれ1咽間隔で1圏角が10個
ずつ、すなわち合計100個になるようにナイフ刃で基
盤目を入れ、セロテープを接着させて急激に剥離を行な
い、塗料が剥離せずに残った目の数を数えた。
9- On this painted surface, make base marks with a knife blade so that there are 10 circle angles at one interval in each direction, that is, 100 in total, and then adhere cellophane tape and peel it off rapidly to remove the paint. The number of eyes that remained without peeling was counted.

また、上記シートを2日間、40℃の温水に浸漬して取
り出して24時間経た後、上記と同じ剥離テストによる
塗膜付着の耐久性試験を行なった。
Further, the sheet was immersed in warm water at 40° C. for 2 days, and after 24 hours had elapsed, a durability test of coating film adhesion was conducted using the same peel test as above.

一方、剛性の評価については、前記のペレットを射出成
形により、4X10Y80各恒の試片を成形し、三点曲
げ試験法(JIS−に7203に準拠)によって曲げ弾
性率を測定した。
On the other hand, for evaluation of rigidity, the pellets were molded into 4X10Y80 specimens by injection molding, and the flexural modulus was measured by a three-point bending test method (based on JIS-7203).

これらの結果を第1表に示す。These results are shown in Table 1.

表中、各配合組成の銘柄は、次の通りである。In the table, the brands of each compounding composition are as follows.

BC3B:三便油(tj−1fエチレン−プロピレンブ
ロック共重合体 TR1ro;シェル化学社製5IS(スチレン/イソプ
レン−21779) TR1107:同上社製SIS (スチレン/イソプレ
ン−14/86) 10− TR1102:同上社製5BS EPO7I):三菱油化社製エチレン−プロピレン共重
合体ゴム HF55;三菱モンサント社製ポリスチ1/ン炭酸カル
シウム;丸尾カルシウム社製 (以下余白) 、11’ ”:II 11−
BC3B: Sanbin oil (tj-1f ethylene-propylene block copolymer TR1ro; Shell Chemical Co., Ltd. 5IS (styrene/isoprene-21779) TR1107: Same as above SIS (styrene/isoprene-14/86) 10- TR1102: Same as above 5BS EPO7I): Ethylene-propylene copolymer rubber HF55, manufactured by Mitsubishi Yuka; polystyrene calcium carbonate, manufactured by Mitsubishi Monsanto; manufactured by Maruo Calcium (hereinafter referred to as the margin), 11''': II 11-

Claims (1)

【特許請求の範囲】 下記の(A) −(D)成分からなることを特徴とする
塗装性の改良されたプロピレン重合体組成物。 ■ 結晶性プロピレン重合体25〜85重量%(B) 
 スチレン−イソプレンブロック共重合体および/また
はスチレン−ブタジェンブロック共重合体3〜30重量
% C) スチレン系重合体2〜5重量% 0 平均粒径0.05〜1.0μの微粒炭酸カルシウム
10〜40重量%
[Scope of Claims] A propylene polymer composition with improved paintability, characterized by comprising the following components (A) to (D). ■ Crystalline propylene polymer 25-85% by weight (B)
3-30% by weight of styrene-isoprene block copolymer and/or styrene-butadiene block copolymer C) 2-5% by weight of styrenic polymer 0 Finely divided calcium carbonate with an average particle size of 0.05-1.0μ 10 ~40% by weight
JP57106353A 1982-06-21 1982-06-21 Propylene polymer composition having improved coatability Pending JPS58222133A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP57106353A JPS58222133A (en) 1982-06-21 1982-06-21 Propylene polymer composition having improved coatability

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Application Number Priority Date Filing Date Title
JP57106353A JPS58222133A (en) 1982-06-21 1982-06-21 Propylene polymer composition having improved coatability

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JPS58222133A true JPS58222133A (en) 1983-12-23

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JP57106353A Pending JPS58222133A (en) 1982-06-21 1982-06-21 Propylene polymer composition having improved coatability

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63277253A (en) * 1987-05-08 1988-11-15 Mitsui Toatsu Chem Inc Polyolefin resin composition
JPS6487645A (en) * 1987-09-29 1989-03-31 Idemitsu Petrochemical Co Polypropylene polymer composition
JPS6490249A (en) * 1987-09-30 1989-04-06 Tsutsunaka Plastic Kogyo Molding resin composition
JPH02238037A (en) * 1989-03-13 1990-09-20 Idemitsu Petrochem Co Ltd Polypropylene resin composition
JPH03157169A (en) * 1989-11-14 1991-07-05 Mitsubishi Petrochem Co Ltd Method for coating resin molded body
US5306548A (en) * 1992-05-20 1994-04-26 The Dow Chemical Company Coextruded weatherable film structures and laminates
US5334450A (en) * 1992-05-20 1994-08-02 The Dow Chemical Company Weatherable styrenic film structures with intermediate tie layer and laminates thereof
JP2006265420A (en) * 2005-03-25 2006-10-05 Okayama Prefecture Olefinic resin composition and method for producing the same
US7341625B2 (en) 2002-03-06 2008-03-11 Sachtleben Chemie Gmbh Method for the production of coated, fine-particle, inorganic solids and use thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63277253A (en) * 1987-05-08 1988-11-15 Mitsui Toatsu Chem Inc Polyolefin resin composition
JPS6487645A (en) * 1987-09-29 1989-03-31 Idemitsu Petrochemical Co Polypropylene polymer composition
JPS6490249A (en) * 1987-09-30 1989-04-06 Tsutsunaka Plastic Kogyo Molding resin composition
JPH02238037A (en) * 1989-03-13 1990-09-20 Idemitsu Petrochem Co Ltd Polypropylene resin composition
JPH03157169A (en) * 1989-11-14 1991-07-05 Mitsubishi Petrochem Co Ltd Method for coating resin molded body
US5306548A (en) * 1992-05-20 1994-04-26 The Dow Chemical Company Coextruded weatherable film structures and laminates
US5334450A (en) * 1992-05-20 1994-08-02 The Dow Chemical Company Weatherable styrenic film structures with intermediate tie layer and laminates thereof
US7341625B2 (en) 2002-03-06 2008-03-11 Sachtleben Chemie Gmbh Method for the production of coated, fine-particle, inorganic solids and use thereof
EP1483336B2 (en) 2002-03-06 2014-09-24 Sachtleben Chemie GmbH Method for the production of coated, fine-particle, inorganic solids and use thereof
JP2006265420A (en) * 2005-03-25 2006-10-05 Okayama Prefecture Olefinic resin composition and method for producing the same

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